Process for cracking and polymerizing hydrocarbons



June 17, 1941. p, SUBKOW 2,245,734

PROCESS FOR CRACKING AN'D POLYMERIZING HYDROCARBONS Original Filed Aug. l2., 1935 2 Sheets-Sheet 1 z'fawf Gas e fst June 17, 1941. P, SUBKOW 2,245,734

PROCESS FOR CRACKING AND POLYMERIZING HYDROCARBONS n Original Fld Aug. 12, 1935 .2Sheets-S'1ieet2 Patented June 17, 1941 Pnocass Foa casema AND' rommmalzme maocaanous rhuip subkow, wat n Annie, cam.. minor to Union Oil Company of California, Los Angeles, Calif., a corporation of California Original application August 12, 1.935, Serial No.

1938, SerlalNO. 218,776

7 Claims.

This invention relates to a process for the formation of high anti-knock gasoline. and particularly to a process for the conversion of low anti-knock gasoline to high anti-knock gasoline are normally gaseous at atmospheric temperatures and pressures, and known as polymerization or synthesis, and processes for obtaining improved anti-knock qualities by molecular rearrangement, known as isomerization.

The conventional process for reforming gasoline consists in subjecting hydrocarbons in the gasoline range, preferably in vaporous form, to high temperatures, under which conditions the gasoline is converted from one having low antiknock properties to one having high anti-knock properties. The gasoline is then separated from the xed gases and normally gaseous hydrocarbons to form a stabilized and reformed gasoline. 'Ihis process for the formation of high iso-octane number material is visualized as proceeding through cracking, dehydrogenating and isomerizing reactions which yield as an intermediate or by-product, low molecular weight oleflnic fractions and chemical radicals with unsatisfied Valances called residuals. In conventional reforming operations there is no attempt to control the subsequent polymerization of these materials to retain and conserve those desirable anti-'knock characteristics and to polymerize the gaseous residuals to liquid hydrocarbons of high anti-knock value. The process of this invention provides for controlled polymerization and conservation of these residuals and oleflns, particularly those of the ethylenic type. in the reaction zones, thus favoring continued decomposition of the petroleum hydrocarbons and increased yield of high octane material over that resulting from a simple reforming operation. A reformed gasoline containing increased percentages of polymer gasoline of high octane value results.

The reactions here generically termed "polymerization include alkylation reactions wherein saturated hydrocarbons combine with un- -saturated hydrocarbons to form high molecular weight branched chain hydrocarbons or alkyla- Divided and thll tllplloltlon July 12,

tion reactions between aromatica and unsaturated low molecular weight hydrocarbons such as ethylene, propene or butene, or straight polymerization reactions wherein oleflns such as mono or dioleflns are polymerized to higher molecular weight polymers. Isomerization, although not strictly a polymerization reaction in the sense that higher molecular weight bodies are formed, is included within this term since it occurs along with such polymerization reactions. The term polymerization" as here used is intended to embrace these types of reactions for building higher molecular weight bodies by reaction of lower molecular weight hydrocarbons. The gasoline produced by this process is termed polymer gasoline, and when produced as a mixture with reformed gasoline it is here termed reformed and polymer gasoline.

The term reforming" is intended to embrace the reactions of cracking or decomposition, dehydrogenation and isomerization by which low octane materialof gasoline or higher boiling range is converted into gasoline fractions of high anti-knock properties.

The object of this invention is to reform gasoline under such conditions that along with the cracking, aehydrogenating, and isomerizing operations there isa parallel, subsequent, or conjoint polymerizing reaction where the gases formed or added to a reforming operation are converted into polymerized materials. and a blend of reformed and polymer gasoline is formed directly in the process. Broadly stated, the invention consists in reforming liquid hydrocarbons, and particularly hydrocarbons in the gasoline range, to produce hydrocarbons having boiling points in the gasoline range and vapors containing hydrocarbons of flve or less carbon atoms, which vapors are polymerized, separately if desired, but preferably in the presence of the gasoline fractions produced by the reforming operation.

The invention also contemplates the addition of hydrocarbons having five or less carbon atoms to the gasoline from the reforming operation and passing to the polymerization zone in order to increase the concentration of these hydrocarbons.

Normally gaseous hydrocarbons such as propane, butane, propylene or butylene may be polymerized. Instead of using the hydrocarbons having four or less carbon atoms, stabilized natural gasoline containing these fractions may be employed. It is preferred, however, to use hydrocarbons of the unsaturated type. Sourses of such gases are processes in which gas oil and/or fuel oil are cracked at temperatures below of feed and by selection of catalysts. In general,

high temperatures, short time, and moderate pressures are desirable. Temperatures may range from 650-1850 F., but the range from 850-1200 F. is preferred. Pressures ranging from atmospheric to 1500 lbs. may be used, but low pressures, as for instance, in the neighborhood of 5-30 atmospheres, are to be preferred. Reforming catalysts for the above process which have been found usful for this purpose are:

Kenia-Nickel, palladium, lplatinum, copper, cobalt. iron, zinc, titanium, aluminum, tungsten, molybdenum, thorium;

Suma-Cobalt, iron, zinc, nickel, manganese, tungsten;

Oxides-Alkali metals such as calcium, magnesium, barium, aluminum, chromium, zinc, manganese, silica;

Hydroxides.-Chromium, alkali metal;

. Acids.-Molybdic, tungstic, chromic, phosphoric, arsenious, silica, boric;

Salta-illuminates, chromates, tungstates, vanadates, uranates, phosphates, of the alkali earth metals such as calcium; and the phosphates, chromates and vanadates of aluminum, chromium or zic; phosphates of molybdenum, tungsten: ammonium molybdate, aluminum-sulfate; adsorbents like fullers earth, bentonite;

Adsorbent charcoal or other adsorbent carbons;

Haldes such as aluminum chloride, iron chloride, aluminum bromide and iron bromide.

When hydrocarbon fractions having a boiling range up to about 60G-650 F. are passed over these catalysts at temperatures from 662-1832 F. a reforming reaction occurs. In producing gasoline containing oleilnic materials temperatures of about 850-1050 F. may be employed. Higher temperatures in the neighborhood of 1380-1830 F. favor aromatic formation. 'I'he salts and oxides of the difficulty reducible metals, as for instance, the alkali metals such as calcium, magnesium, barium, 'require in general higher temperatures for the formation of oens, i. e. temperatures in the neighborhood of 1020-1380 F. The gases ,resulting may then be reacted in the presence of a polymerizing catalyst.

Catalysts which have been found to aid polymerization are termed polymerizing catalysts. Such catalysts are fullers earth, absorbent carbon, phosporous acids such as orthophosphorous acid, and phosphoric acid such as othophosphoric acid. In solid form, aluminum oxide, calcium oxide, carbonates of the alkaline metals, the oxides and carbonates of magnesium or beryllium, the acids of boron and anizimony,` thoria, zinc chloride or aluminum chloride, cadmium phosphate, aluminum sulfate in solid form, absorbent clays like bentonite, graphite, charcoal, copper, alkali metal salts (especially oxygen-containing salts), phosphates, borates, antimonates, boron triiluoride, either alone or as a double compound with ethylene in the form of ethylene uoboric acid, cadmium phosphate, and siliceous earths, tin, zinc, aluminum, chromium, silicon, leadv or alloys of these metals.

In using the reforming and polymerizing catalysts, o ne skilled in the art will understand that the conventional methods of preparing catalysts of this nature are to be followed. Thus,

the metals are best used what in finely divided form, and better when .lupported on carriera. For example, the metal'might be formed by reducing the oxide of metal absorbed upon a carrier suchascharcoalorsilicagelinastreamqf hydrogen. These methods are weil known and conventional in the catalytic art. The salts or acids are best formed when precipitated on a carrier or fused with a carrier and ground into a line state. The clays such as bentonite and fuller's earth are best used in their activated states, thus fullers earth is used in the acid treated state, in which state their absorptive activity is best brought out. Methods of increasing the absorptive activity of clays and absorbent carbon are well known in the absorption art.

In using catalysts to be carried in the stream of gases, the catalyst, if it is boron iluoride.may befedasagas tothisstreamormixedinthe liquid state at low temperature. If the catalysts are solid they are best ground fine and carried in suspension by mixing with the liquid feed and carried along by the high velocity of the vapors. The solid catalysts may also be positioned as a contact mass in the reaction zone and the vapors passed through the body of catalyst.

The reactions which have been termined polymerization reaction," and reforming reaction are parallel reactions. These reactions are generally reversible, the reaction in one direction being a'polymerization reaction, and the reaction in the other direction being a reforming reaction. Consequently, in the polymerization operation and in the reforming operation, all reactions may occur. In general, the polymerization reactions are favored by lower temperatures, while the reforming reactions are favorable by higher temperatures, the temperatures chosen should be those at which the desired reaction predominates. 'I'he temperature will also vary with the feed stock, particularly upon its boiling range and the chemical type of the feedstock and with the pressure. An additional factor is time. The polymerization reactions and decomposition reactions may proceed further by allowing a longer time of contact with the catalyst. Care must be taken to prevent the reforming reaction from going too far, thus forming light, undesirable fractions, or from allowing the polymerization reaction to form undesirable heavy bodies by too long a polymerization contact time.

Various catalysts promote one or the other reactions/favorably, under certain temperature conditions. 'I'he temperatures and pressures herein disclosed are merely illustrative and are those at which the various reactions predominate, but the opposite reaction, whether it be reforming or polymerization, also occurs. The temperatures are merely illustrative and are for feed stocks as herein described, and for pressures from atmospheric to 5000 lbs.

Thus, with metal catalysts, tin, zinc, copper,

aluminum, chromium, silicon, lead and nickel favor polymerization reactions in the temperature range between 350 and 700 F. Nickel favors the reaction in the lower of the said range, that is, around 350455" F. Thesematerials favor the reforming operation at higher temperatures. Iron and nickel favor the polymerization operation above about 390 l". and in general, iron, nickel, copper, cobalt, zinc, aluminum, chromium favor the reforming operation at temperature ranges above 932 F.

It will be seen that certain of the materials here recited, for example, both zinc and nickel action is' favored at temperatures above 930 shown above, itis preferable that polymerization i reactions be carried out at lower temperatures here indicated, and the reforming operations at the higher temperatures. However, by applying higher pressures as hereinafter described, the reaction temperatures are brought closer toi gether and polymerization and reforming may occur together at the sam'e temperature.

Catalytic oxides used for these reactions, such as aluminum oxide either alone or combined with silica in the form of aluminum silicates, for ininstance, oridin or fullers earth, favor polymerization in the temperature range between 570 and '150 F. Preferably, aluminum oxide should be used in the neighborhood of from 640 to 700 'F. Lime and other alkali earths or Oxides or carbonates favor polymerization in the range between 660 F. and 840 F. Magnesium and beryllium oxides favor polymerization reactions in the upper part of said range around 840. F. to 930 F. Aluminum chloride and boron trifluoride are very active at temperatures from 32 F. to 300 to 390 F. Magnesium oxide-lime and silicia, such as silica gel, can be used in reforming reactions in temperature ranges above 930- l290 F. Aluminum Ioxidor aluminum silicate such as fullers ,eartlor floridin or other forms will favor reforming above 750 F. Thus in using aluminum oxide, either alone or in the form of silicate, the temperature ranges should be adjusted depending on the form of the reaction which is to be favored. In operating in the upper ranges around '750 F. aluminum oxide will have a favorable influence on both reactions, aiding in the decomposition in the higher molecular weight liquid hydrocarbons, and aiding in the polymerization of lower molecular weight gaseous hydrocarbons. The temperature range should be chosen to form a balance between the two.

Of the salts or adsorbents which accelerate polymerization reaction, the alkali metal carbonates, phosphates and borates are active in the neighborhood of 'Z50-930 F.; bentonite is active from G60-840 F.; phosphoric acid is active from 35o-475 F. Absorbent charcoals and carbons favor the polymerization reaction at around 750 F. Above these temperatures, and particularly at substantially higher temperatures reforming is favored by these catalysts. Calcium aluminate and ammonium molybdate favor the reforming operations at temperatures of 930- 1290 F. and higher. Aluminum sulfate and phosphoric acid are active in reforming reactions above 660 F. and very active above 930 F.

Mixed catalysts composed of mixtures of any one or more of the above reforming catalysts, and any one or more of the above polymerizing catalysts, which are active, i. e. promote and accelerate the reforming and polymerizing operation in the neighborhood of TO-930 F. will permit of the joint and favorable reactions of reforming and polymerization when operated vat temperatures between about TO0-930 F. at pressures of about '75-1500 lbs.

Higher pressures favor the polymerization reaction and therefore, by the amplication of pressure, the tolerable temperature for polymeritends to decreasethe reforming operation,v and 'the two operations may beubrought closer together by the application of pressure. -By choosing a temperature intermediate the preferred reforming and polymerization reaction temperature at atmospheric pressure, and applying high pressure in the neighborhood of 1000- 5000 lbs. lthe samp 'catalyst may be used for both reactions.'- It may be chosen to use a catalyst or catalyst mixtures whose temperature at which they accelerate the reforming operation, and the temperature at which they accelerate the polymerization operation, do not lie far apart. Thus, for instance, one may choose catalysts which are active, i. e. promote or accelerate, in reforming at temperatures in the neighborhood of 840- 1060 F., and choose catalysts which are` active in, i. e. promote or accelerate, the polymerizing reaction at temperatures ranging from about 570-840" F. at pressures ranging as low as atmospheric.

The liquid gases may be washed with alkali to Ifree them of hydrogen sulfide and they can then be charged. The charging stocks to the reforming operation may contain organic sulfur bodies which will poison the catalyst. One may either remove these bodies or use a catalyst which will not be poisoned in these bodies.

The following of the above referred to catalysts are not easily. poisoned by the sulfur and sulfur bodies presnt in the charging stocks here used. Metals: Cobalt, iron, zinc; suliides of cobalt, f iron, zinc, nickel, manganese, tungsten; oxides of chromium, zinc, manganese, aluminum; chromium hydroxide; molybdic, tungstic, chromic, phosphoric, arsenious, silicic, boric acids; phosphates of alkali metals, molybdenum, tung?V sten; ammonium molybdate, aluminum silicate, fullers earth.

Water and oxygen and traces of alkali poison aluminum oxide and fullers earth catalysts. Small percentages of moisture in such catalysts as hereinafter described may be tolerated.

. Oxygen also poisons aluminum oxide, fullers earth, and the metal catalysts. Air should be excluded."

A good catalyst for the polymerization reaction is aluminum oxide preferably in the form of fullers earth or artificial fullers earth formed by co-precipitating silica and aluminum oxide from a mixture of sodium silicate and aluminum sulfate. The aluminum silicate is washed neu tral and dehydrated. It is preferred that the mixture be neutral or acid, and free of alkaline material. It is best that the catalyst be substantially free from water, dehydrated by heating, although a small percentage, up to 5 or 6% of moisture is not detrimental. In using this catalyst it has been found that a small amount of hydrochloric acid introduced as alkyl chloride, as for instance, isopropyl` chloride may be introduced to aid the polymerization reaction. Ap-

' parently, the isopropyl chloride is decomposed in the reaction zone and forms free hydrochloric acid.

It has been found that the alkyl chlorides are conveniently formed by passing a mixture of unsaturated hydrocarbons such as butylene and propylene over the above fullers earth type catalysts as previously disclosed at ordinary temperatures from about 20D-400 F. The alkyl chloride may be introduced either iirvapor form as produced by the chlorinating reaction, or rst condensed, and then introduced in liquid form.

The catalysts here :employed may be used in the reforming or polymerizing processes either asacatalystbodyorasamixturewithincoming feed. In using the catalyst as a catalyst body, the reaction zone in the tube or chamber is charged with the solid catalyst and the'reaction vapors are passed through the body of the catalyst. It is possible, however, to use the catalyst as a slurry with the incoming feed, in which case the reaction zones are empty except for the reaction mixture. When the vaporized hydrocarbons carrying the catalyst ground fine in suspension ypass through the reaction zone, the high vet locity of the vapors and the fine particle size of the catalyst prevent sedimentation of the catalyst in the tubes or chambers.

In carrying out the process of this invention the following principles may act as a guide. 'I'he feed of liquid fractions is one preferably having an end point not in excess of 650 F. Usually a heavy gasoline fraction boiling between 300500 F. will prove satisfactory. The reforming, cracking or dehydrogenation is 'best carried out at a temperature plane higher than that at which the polymerization reaction is carried out. It is desirable also to control these reactions so that they do not proceed to the ultimate stage of carbon, hydrogen and methane formation or to the production of high boiling fractions in the iuel oil range. It therefore will berdesirable in one form of this invention to u"se relatively high temperatures and short times of contact in the reforming zone, and to cool the reaction products produced by the dehydrogenating and'cracking reactions before passing them to the polymerization reaction zone. vThe yield of polymerization products may be increased by adding to the reaction mixture from an extraneous source hydrocarbon materials of five or less carbon atoms. 'I'he polymerizing reaction including addition of unsaturates to unsaturates and alkylation in .poly-molecular reaction is favorably influenced by increasing the concentration of the reactants. This may be accomplished by increasing the pressure, and also by adding materials undergoing polymerizing reaction to the reformed vapors. These may be cracking still gases, or liquid gas from a gasoline stabilizer tower.

It is desirable to have present unsaturated hydrocarbons such as butenes, propenes and ethylene. The gases may be obtained from the cracking of gas oil or fuel oil at temperatures from 850- 1000J F. and preferably, from 90o-950 F. 'I'he gases are those produced after the cracked gasoline has been removed. Other processes for producing these unsaturates may be employed to produce the unsaturated normally gaseous hydrocarbons here added to the polymerization and reforming operations, as herein described. 'I'he saturated normally gaseous hydrocarbons under go dehydrogenation and polymerization during the reforming operation. 'I'he decomposing reactions occur best at low pressures, the polymerization athigher pressures. It therefore may be desirable to increase the pressure in passing through the polymerization stage. 'I'he diiiculty of compressing hot vapors makes this step practically difficult. It is, therefore, desirable to compress only the cold feed and to operate the whole system under the desired high pressure for the polymerizing reaction. The use of catalysts per. mits the use of lower pressures for the polymeriz- '111e amount Aof valkyl chloride required varies ing reaction 'and lower temperatures 'for the refrom one-tenth to one per cent, preferably to forming reaction than would b e possible without about 'one-halfpercentof the reaction vapors. the catalyst.

While the processes of reforming and polymerization are two distinctprocesses which may be separated the one from the other by careful choice of conditions and catalysts lby control of conditions, as previously. described, the two' processes may be interwoven.

In operating a combination of reforming and polymerization such as, for example, those shown in Figures 1, 2. 3 and 5, where saturated normally gaseous hydrocarbons are introduced into the reforming zone. this reforming may be operated at a relatively high temperature to form larger amounts of unsaturated normally gaseous hydrocarbons in the vapor mixture passing to the polymerization stage. In such a process an activedehydrogenating or reforming catalyst may be employed. The temperature to be employed may be in the upper portion of the range suggested for the reforming catalyst. Another procedure to be followed in this connection is to carry the reforming on at relatively high temperatures to Produce large amounts of gas by extensive cracking of the feed stock. Thus, for instance, in operating on a charging stock composed of crude gasoline of from 45o-500 F. end point, the cracking may be carried on to produce large gas yields in excess of 40o-500 cu. ft. per barrel of charging stock. These gases, together with any added gas may be passed to the polymerization stage. In this connection the gasoline fractions may be first removed and the lighter gases polymerized or .the polymerization may be carried on in the presence of the reformed gasoline fractions.

The cracking and dehydrogenating processes of reforming are reversible reactions, and concomitant with them occur polymerizing and hydrogenating reactions. The unsaturated bodies formed as a result of the cracking and dehydrogen-ation are extremely active and tend to combine with each other. 'I'he light unsaturated gases tend to polymerize with themselves and with the unsaturated higher molecular weight bodies present in the reaction zone. It is therefore possible to combine the reforming and polymerizing processes and to cary on the polymerization of the lighter fractions (five carbon, and particularly four carbon and lower) in the presence of the hydrocarbons within the gasoline range formed as a result of the reforming operaftion. By such a combined process, the low molecular weight olefinic products of the reforming processes are continuously and progressively removed by polymerization from the reaction zone as they are formed, thus favoring continued reforming of the petroleum hydrocarbons and an increased yield of high octane material over that resulting from a simple reforming operation. 'I'he lower molecular weight unsaturated hydrocarbons, particularly those of iive carbon atoms and less are polymerized with themselves and are also polymerized by addition of the higher molecular weight liquid hydrocarbons of six carbon atoms and more formed in the reforming reaction, or present in the hydrocarbon -material forming the charge to the operation.

If desired, instead of using a mixture of catalysts, the catalytic zones may be separated and the reaction mixture pased separately or alternately over a dehydrogenation and polymerization catalyst. This may be accomplished by passing the mixture through a series of tubes of the return bends and the tubes filled alternately with a dehydrogenation anda polymerization catalyst in a number of runs so that the mixture is reformed and polymerized in repeated passages over the catalyst. The tubes may be placed in a furnace and the temperature and pressuremaybe uniform throughout the tubes oi' the tubes may be placed in reaction zones of 'different temperatures. the reforming tubes being. at higher tem-l peratures than the polymerization tubes. The reaction mixture is then heated and cooled. first heated to the reforming temperature in the reforming tubes. then cooled to a lower polymeriz ing temperature in the polymerization zone. If desired, temperature alone may be used to produce the desired reforming and polymerization without using catalysts in the tubes.

While catalytic operations are preferred, certain of the advantages of this operation are preserved in non-catalytic processes thus either the reforming or polymerizing reaction or both may be operated without the aid of catalysts to obtain a great number of the advantages of the operation.

Another arrangemen-t which may be used is to carry out the process in a heated chamber through which are passed cooling tubes. Cracking and dehydrogenating catalysts may be deposited on the warm walls of the chamber, and polymerizing catalysts on the cooler tubes.

If desired, air may be passed with the vapors through the cracking and dehydrogenating zone in such cases where the oxygen or water vapors will not have a poisoning action on the catalyst, in order to remove undesirable gum-forming con. stituents such as diolefln. Olens other than .those that react readily with free oxygen are not objectionable constituents in gasoline, and their conservation is desirable. Retention of these desirable unsaturated compounds may be accomplished by a controlled polymerizing action which only affects those unsaturates which are most readily polymerized and leaves the others to contribute their high anti-detonating characteristics to the fuel.

The process of polymerization and also of reforming results in a product which is composed of a polymer and reformed gasoline fraction of high octane and having an end point of from 3D0-400 F. depending on operations, a heavy gasoline-kerosene fraction having an end point of about 50o-55W F. and a heavy portion. The heavier fraction called heavy gasoline-kerosene is recycled. While the figures describe the total return, it will be understood that only a portion may be returned and the remaining portion sent to storage or re-run on blending stock with the polymer and reformed gasoline.

It is therefore an object of this invention to subject kerosene and gasoline and heavier petroleum fractions to a reforming operation in the presence of a reforming catalyst.

It is a further object of this invention to form a reformed and polymer gasoline by subjecting gasoline, kerosene and heavier hydrocarbons to a reforming process and to subject light hydrocarbons to a polymerizing reaction to form a polymer gasoline, and to combine and rectify the two to produce a reformed and polymer gasoline.

It is another object of this invention to subject gasoline and kerosene and heavier petroleum fractions to a reforming operation in the presence of a catalyst which will aid the polymerization oi' the lighter hydrocarbon fractions, and particu- "antenas nature of cracking tubes connected togtberby larlysthcse whicharenorxnally'gascous in the reforming operation. s

It is a mths;- oblepct or uns invention to ubiect gasoline and kerosene and heavier petroleum fractions in the presence of a normally gaseous hydrocarbon to vs. reforming and polymerization reaction, preferably in the 'presence of catalystswhichwill accelerate and aid the reforming and polymerization reactions. v

It is a further obiectof this invention to subject gasoline and kerosene and heavier petroleum fractions to a reforming operation and then to subject the product of the reforming operation to a polymerizing reaction, preferably in the presence of a polymerization catalyst.

'It is a further object of this invention to sublect gasoline andkerosene and heavier petroleum fractions to a reforming operation, and then to subject the product of the reforming operation in the presence of added normally gaseous hydrocarbons to a polymerization reaction, preferably in the presence of a polymerization catalyst.

It is a further object of this invention to subject gasoline and kerosene and heavier petroleum fractions to a reforming and polymerization reaction in the presence of a reforming and polymerization catalyst under such high pressure conditions andr such conditions of temperature that the polymerization and reforming operations are both aided by the presence of the polymerization and reforming catalysts.

It is a further .object of this invention in subject gasoline and kerosene and heavier petroleum fractions to a reforming operation and subsequently to a polymerization operation under such conditions of temperature and pressure that the reforming operation is carried out at a higher temperature than the polymerization operation wherein the reformed gasoline composed of gasoline and kerosene fractions, and containing normally gaseous hydrocarbons are subject to a lower temperature for polymerization of the polymerizable hydrocarbons at that temperature and .pressure.

This invention will be better. understood by reference to the subjoined figures in which:

Figure 1 is a flow sheet showing the polymerization and reforming reactions and providing for withdrawal and the addition of a catalyst at an intermediate point in the reaction.

Figure 2 shows a stage reforming and polymerization reaction in which a promoter is addedY to the reaction undergoing polymerization;

Figure 3 shows a stage polymerization and reforming reaction wherein provision is made for the control of temperature in the polymerization reaction;

Figure 4 shows a combined polymerization and reforming operation;

Figure 5 shows a design 4and flow'sheet of a combined polymerization and reforming operation and a furnace structure for the control of temperature in the various coils of the furnace;

Figure 6 showsa simultaneous polymerization and reforming operation wherein the polymerization and reforming operations are carried on separately, and the products are combined and treated together.

Figure 1 represents a schematic flow sheet of a combined reforming and polymerization process in which the reforming is primarily conducted in one zone at relatively higher temperature and polymerization in another zone of relatively lower temperature. In Figure 1 gasoline, kerosene, or gas oil fractions having end points under 60G-650 F. to be reformed are fed through line Iby pump 2 through valve 3 and line I into the reforming coil 'i in furnace l. The reforming catalyst may be added before passage to the heating coil through line l controlled by valve t. The mechanism for the addition of the solid catalyst to the oil stream is shown schematically as indicated. Mechanisms for the addition of solid material to liquid being well known in the chemical engineering art. The reforming catalyst may be one of the previously mentioned catalyst or may .be a mixture of reforming and polymerization catalysts. The temperature of the reforming operation will be chosen to correspond with the cata- 4 lyst used in accordance with the principles hereinabove discussed.

'Ihe reforming stream containing the catalysts may be treated in one of two ways. If the prior reforming operation was made in the presence of a catalyst or catalyst mixtures different from those which it is desired to have present in the polymerization zone, the stream is -by-passed by closing valve Il and opening valves Il and Il. The stream of catalyst and oil vapor is then passed through line I and meets oil residuum such as fuel oil entering at Il to act as a dousing medium to wash out entrained catalysts and separate the vapors from-the dousing medium in the Separator I2. The temperature maintained in the separator is about 500 F. to insure the vaporizatlon of the gasoline fractions. The mixture of oil and catalyst is removed through valved controlled line i3, and the vapors of gasoline and lighter fractions including the hydrocarbons of four and less car-bon atoms, pass through line l5 and valve Il into line l. However, if it is desired that the catalyst present in the reforming coil 1 and catalysts entrained in the vapors passing therethrough -be also present in the polymerization zone, valves Il and II remain closed and valve Il is open. In the event the operation in chamber I2 is carried out, additional catalysts may be added through line l1 or provided as catalytic mass in the reactor chamber 2l. It may be found desirable to add fresh catalysts to the reaction mixture. Also, in the event that the operation in chamber I2 is not carried out, the reaction mixture passes through line 9' in order to increase the concentration of active catalysts in the reaction mixture.

The reforming operation may be carried out with the omission of catalyst introduction through I, and the entire reformed mixture may be passed either through Il or by-passed to I2 and the separated gasoline sent to reactor chamber 29 in the same manner as previously described. The catalyst added through I1 is preferably chosen from among the polymerization catalysts herein previously disclosed. In order to increase the concentration oi' light hydrocarbons there may be added through line il liquid gases produced in the stabilizer as will be hereinafter described. There may be also added at this point liquid gases from an extraneous source through line 2| and pump 22. 'Ihese gases are preferably propenes, butenes, ethylene, or mixtures of these hydrocarbons with the saturated hydrocarbons of four or less carbon atoms. The mixture is formed in line l'. In the event that the cooling operation in chamber i2 and the cooling effected by the addition of the liquid material through line It and vaporization of this material has reduced the temperature below the chosen reaction temperature, the mixture may be by-passed through line 23 andreheatingcoilllinfurnacelbytheproper manipulation of valves ia, 2l and 21a. This control heater will then adjust the temperature in line 2l to the proper reaction temperature to 'be maintained in reactor 2l. In the event that the reactor does not contain the mass catalysts in the form of acontact mass in the chamber. it becomes merely a reaction chamber to give reaction time to the mixture. In operating the reactor without the catalyst mass it would be advisable to directA the iiow of vapors and entrained catalyst downwardly by adjusting the valves 28a in lines 28 and valved line 2l' and valves Sla and 32a in line Il so that the iiow will be downward through the reactor and into fractionator '33. If the catalyst contact mass is used, it may be desirable to flow the vapors upwardly through the reactor and in which case by proper manipulation of the valves 2.a. 20a, lla and 32a, the ow may be properly directed. Gasoline thus formed will result from the reforming reactions operating on the charge to coils' l and on polymerization of the reformed vapors and gases.

The reformed and polymer gasoline then passes through fractionator Il containing the usual reflux cooler 42 which may be either internal or external. The heavy fraction, containing the suspended catalyst if this is combined in the vapors is removed from the tower through line 34 controlled by valve Il. 'I'he heavy gasoline fraction is removed through line pump I1 for recycling to the reforming operation via line I8 or is removed from the system partially or totally. The reformed and polymer gasoline is removed through side stream take-oi Il into tank 39, passed by pump Il through heater 4I and line 45 into the stabilizer 48. Uncondensed gas from the fractionator passes through line 4I. compressor 43a and line M into the stabilizer ll. The gasolines'and gas are separated into a stasbilized gasoline removed through line Il, valve 52, and cooler 53 and the liquid gas fraction containing butanes, butylenes, propanes, propylenes, some ethane and ethylenes in liquid form pass into tank 5I and circulate by pump 51 through line 2li as previously described. Heat is supplied to the bottom of the tower by circulation from a lower tray through line l1, heater and returned through line il. The uncondensed and fixed gases are removed through line 54,- controlled by valve i5.

'I'he conditions to be maintained in heater 1 and in the reactor 29 are those previously described and must be adjusted for the stock and catalyst employed as will be well understood in the art.

In carrying out the process shown in Figure 1, any one of the catalysts here described may be employed. but the flow will be explained using one of the catalysts merely to illustrate the principle of carrying out the reaction.

It will be understood that the other catalysts may be used with the proper control of temperature and pressure according to the principles hereinabove fully described. A

A kerosene 'fraction having an end point of about 550 F. is passed through line l and is intimately incorporated to form a slurry with molybdic acid, molybdenum sulfide, or calcium aluminate, and is heated to a temperature of about 930 to 1290" F. in coil 1. The mixture is then passed through line 8 into chamber I2 in which the catalyst and the oil are withdrawn and the vapors at a temperature of about 450 F. are

ber 29 which is charged with a phosphoric acid- I catalyst in the form of orthophosphoric acidl deposited upon a fuller's earth base. The pressure maintained in the coil 1 and the chamber 29 is about 500 to 1000 lbs.

Figure 2 shows an operation of reforming and polymerization wherein the reactions occur in the presence of an activating material which acts as a promoter to the reaction, or in the presence of an extraneous material which aids in producing improved characteristics in the final product. Vis/previously described the'catalysts may be either added to the material entering the reforming operation or present in the reforming tubes or may be placed in the polymerization reactor. catalysts, it passes together with the catalysts through the polymerization reactor. It has been found that on using polymerization and reforming catalysts of the adsorbent clay type, such as fullers earth or on using base catalysts like aluminum oxide, hydrochloric acid gas or alkyl chlorides which react at the temperature reaction in the presence of these catalysts activate these catalysts. It has been found additionally, that these alkyl chlorides are themselves quite readily polymerized into higher molecular weight hydrocarbons or chlorinated hydrocarbons. While this polymerization is shown as occurring in a catalyzed reaction, the alkyl chloride with or without mixture with the hydrocarbon feed as here shown, may be polymerized in tubes 1 in an uncatalyzed reaction. The action in reactor 29 if desired may be catalytic or the end product of the uncatalyzed polymerization in 1 may be digested to aid polymerization in chamber 29 free of catalyst.

In carrying out the process shown in Figure 2 the feed is described as being made up of gasoline fractions to which may be added the alkyl chlorides. .It is of course possible that the feed may be composed of alkyl chlorides alone. However, it is preferred to operate the process in Figure 2 whereby the alkyl chlorides are added to the gasoline and in the event the alkyl chlorides are used as a promoter in the catalytic polymerization reaction they will be added to the reaction mixture entering the polymerization zone. Heavy gasoline or kerosene passes through line I, pump 2, to be passed with stock added through valve 3 and pass then into line 4 and valve 3 into reforming coils 1 in furnace 8. Alkyl halides may be fed through line 60 and valve 60a into reaction coil 1, or in the event that the feed is composed entirely of these halides, material is not introduced in line I. If it is desired instead of feeding halides through line 60, valve 60a may be closed and the halldes may be introduced into line 9. Polymerization catalyst is introduced into the stream passed into line 4 as previously described by any well known solid feeding mechanism. The point of introduction should be prior to the introduction of the stream into coil 1 unless the cata.- lyst is contained inside the coils. Reformed material passes through line 9. Before entering line 9 it meets liquid gas introduced through line I8. These liquid gases may be introduced from stabilizer 46 as later described or may come from an extraneous source or may be both. The reactor 29 may be used either as an additional contact catalytic zone in which case the catalyst is maintained in the reactor as a contact mass or If the gas stream contains i the reactor may be empty'and merely provide reaction time. The material passes through line 9 controlled by valve 9a and through the reactor 29, vpasses through line 32 and valve 32a, to fractionator 33. In the event that reaction is com-L pleted in coils 1, reactor may be by-passed by closing valves Safand 32a and the vapors passed through line 3|, controlled by valve 3Ia directly into fractionator 33. In mictionatorv 33 material is separated into a heavy residual fraction and is withdrawn through line 34. The bottoms are reheated by circulation through lines 23, pump 23a, heater 26 andline 21. Incompletely Iconverted gasoline is withdrawn through line 36 and pump 31- to act as recycle stock aspreviously described. The reformed and polymer gasoline is withdrawn through line 38 into tank 38 and passed through pump 40 and heater 4I to stabilizer 4-6.` The gases uncondensed by cooler 42 pass through line 43, compressor 43a into stabilizer 46. In stabilizer 4-6 the gasoline and gases are separated into a stabilized, reformed and polymerized gasoline which is' withdrawn through line 6I and cooler 53. Bottoms, are circulated through line 41, heater 4 9 and line 50 to prov ide heat in the base of the column. Liquid fractions composed of butane, butylene, propane, propylene, ethane and ethylene are withdrawn in liquid form into tank 56 and passed to line 20 into line 6I as will be hereinafter described. The uncondensed and xed gases are withdrawn through line. 64 controlled by valve 55, cooled and condensed to provide a reflux to column 46. The liquefied gases are withdrawn through line 20 to which may be added from an extraneous source, preferably unsaturated normally gaseous hydrocarbons or mixtures of said hydrocarbons and saturated normally gaseous hydrocarbons. The gases may be separated in the following fashion: A portion may be introduced through line I8 and valve IBa as previously described. Another by valve 6Ia to the reaction chamber 62 for conversion into the halide.

bons in the nature of propylene, butylene, amylene will react with hydrochloric acid in the presence of activa-ted fullers earth or aluminum oxide at temperatures from 32-390 F. to form alkyl halide. Propylene will add in the presence of hydrochloric acid at temperatures from 32- 390 F, to hydrochloric acid very smoothly. The alkyl chloride thus formed may be introduced into the reaction stream by passing through line 63, valve 64 and line 65. In passing through 65 it passes as a vapor and may be introduced into line 9 to activate the polymerization in reactor 29. It has been found that as much as from one-tenth to ve-tenths percent of isopropyl chloride when added to the gases entering the polymerizer reactor chamber 29 accelerates polymerization reaction markedly. The chloride may be passed via line 60 and valve 60a into coils 1. Instead of passing the isopropyl chloride as a vapor the isopropyl chloride may be condensed by passing through line 63a, valve 64 remaining closed to cooler 66, collector 61 and uncondensed gases may be removed through valved line 68; the condensate is fed by pump 69 through valved line 10 as previously described. The hydrochloric acid may be added into the stream entering the reactor 62 through line 1I. In operating in the presence of isopropyl chloride, it would be advisable to insu-re that the gases and liquid are moisture free. Provision will have to be made for lseparating free hydrochloric acid from the gases in 84 and from the various condensates withdrawn from the system by treatment with sodium Reaction chamber 82 is charged with activated` fullers earth or aluminum oxide as previously described. The material entering line 4 is a slurry of this catalyst and oil, the temperature maintained in reactor 82 is as described, under'` 390 F. "Dry hydrochloric acid gas is fed through- 1I and) alkyl chloride is introduced into line I8.v

The temperature maintained in reactor 1 is in the neighborhood of 930-1020" F. and the temperature in' reactor yza is from aio-'130 r'. 'rms rature is maintained by the introduction of mate a1 through I8 or through cooling the gases /xzeringsthrough 8 by an interchanger, as Willi be understood although not shown in the drawings, or by the control in the reactor 28 as shown in Figure3. Cooling in line 8 may be provided as shown in Figures 3, 4 and 6.- Pressure maintained in reactors 1 and 28 is in the neighborhood of 50o-,1500 lbs.

Figure 3 shows schematically a combined process of reforming and polymerization process in which separate reforming and polymerization zones are provided. A reforming zone is -provided in coil 1 in which coil polymerization may also be effected if desired. Provision is made for the control of the temperature in the polymerization zone 28. The polymerization, being exothermic, the temperature in the reaction chamber 29 tends to rise, and it isdesirable to control the temperature to prevent excessive increases in temperature.

Feed is introduced under pressure through line I and may pass either through line la' and valve 2a or through line Ib and valve Ic, or through both to the reforming coils 1. It is preferred, in the event that. the feed is a mixed feed contain- Ulv motions is sided by me introduction of nxd gases -such as hydrogen, methaneycarbon di-v oxide or liquid gasesused in the polymerization reaction 'in chamber l2. With some catalysts where Asteam is either anaid or is not a detriment to the polymerization reaction,l steam maybe ing a wide range of boiling fractions such as gasoline, kerosene and gas-oil, to rectify the feed by introducing it through line Ib and valve Ic into the fractionating chamber 33. In this chamber it meets the hot vapors from the reaction zones and aids in the fractionation of these vapors to form a heavy residual fraction 28 composed of the heavy ends of the charging stock and the heavy ends of the polymerized and reformed gasoline. A side cut of intermediate boiling fractions is removed through line lsb and circulated through line I8 to meet any portion of material by-passed through line la if any such is by-passed. If desired, a portion of the liquid gases which are to be polymerized are introduced through line 88 and the mixture is then passed through line Ia, heat exchange coil 8a, line 4 into the reforming coils 1 positioned in furnace l. At the outlet of coil 1 the reformed gasoline is doused by contact with relatively cold heavy oil such as fuel oil entering through line II and the partially cooled gases are then passed through heat, exchanger 8b from which point they may be/passed directly to the polymerizing chamber 28 via line 8', or first passed through the separator I2. In separator I2 the heavy ends are removed through line I3 and the vapors withdrawn from line |81/ The stripping of the bottoms to insure the removal of the gasoline used at this point. A spray of ywash oil Ila is passed over the mist extracton and fractionating elements I2b to insure separation of entrained materials and heavy ends of the vapors. Instead of passing the vaporsy through this chamber. the chamber may be by-passed by proper control of valve I0 in linel and valve 0a in line 8' to pass the vapors around the separator. The vapors are then passed to the polymerizing zone 28. Instead of passing the gases through the reforming zone, or in addition to passing the gases y through the reforming zone,`they maybe added to the vapor in line 8 through by-pass line I8 by proper control of valve 18a' and valve 88a. The mixed gases and vapors are then passed through line 8 into the reaction zone 2l. l

In order to control the temperature in the reaction zone 28, the liquid gases may be expanded through spray 8| by proper control of valves 82 and also by circulation of cooling iluidthrough the cooler 88 via lines 83a and 88h. In operating the` separator I2 in such manner that only the light fractions of gasoline are separated, the temperature'of the outlet vapors may sometimes be I below the desired temperature in the polymerization chamber 28. Thus for instance, the vapors issuing through line I 5 may be in the neighborhood of 400-450" F. while the reaction zone may be of a temperature of 600 F. and above. Under `those circumstances it may be desirable to heat the reaction chamber 2l instead of cooling it. To do this the cooler 8l may be converted to a heater by circulating a heating fluid through the coils of the cooler 83. This cooler may be of the closed tube sheet type, the cooling fluid circulating out of contact of material in the reaction chamber 28. The gases entering through valves 82 and spray 8| may be heated by passing through valves 84 and 86 and heater 88 by the proper manipulation of valve 81'. Any desired proportion of the gases to be added for polymerization may be added in this way. Such gases thus added are not subject to the reactions occurring in the reforming coils 1. If it is desired to polymerize these gases without subjecting themto the reforming operation all the gases may be introduced in this manner.

The heavy polymers formed in the reaction zone and which are not volatile at the temperture in chamber 28 are withdrawn through 34a and the vapors are withdrawn through line 34 to be passed to fractionator 38. There they pass countercurrent to the feed Ib and the reflux formed by cooling coils 42. In addition to the heavy cut lsb, a reformed and polymer gasoline is withdrawn through the side cut into tank 39 and passed by pump 40 through heater 4I into the stabilizer 46. The uncondensed vapors pass through line 43, compressor 43a into the stabilizer 48. In the stabilizer, the gasoline is separated into a stabilized gasoline, 'withdrawn through 5I and cooler I8. The bottoms are reboiled by circulation through line 41, heater 48 and return lineBII. A liquid light hydrocarbon fractionwithdrawn through line 88a into chamber 56 and composed of the fractions containing four or lower carbon atoms, both of the saturated and unsaturated types. Fixed gases are withdrawn through line I4, condenser Mb and recycled as a reflux through line 54a. The liquid gas is circulated through line 20 by pump 51 and meets additional gases through valve 81 coming from storage 89. rIhese liquid gases are similar to those in 20 and are derived from other refinery sources. These gases may be sent through 1ine88' or 80 as previously described.

' In operating the process according to this flow sheet the temperature in coil 1, may be from 60o-1000" F. Thus, for instance, it may be operated atabout 980 F., cooled by the dousing medium to about 650 F. and further cooled to about 500 F. and separated in I2. Vapor withdrawn through line may be in the neighborhood of 425 F. and the chamber 29 maintained at about 600 F. In employing a catalyst requiring a polymerization temperature of 350-450 F. the reaction chamber is cooled. Catalyst may be omitted in the reforming operation and the temperature then employed may be from 9501200 F.

The reaction shown in Figure 2 may also be carried out in Figure 3 in which case the reforming catalysts may be fed as a slurry in line 4, separated in chamber I2, and the polymerization catalyst be disposed as a contact catalyst mass in chamber 29. The temperatures and pressures discussed with relation to Figure 2 may be applied to the process of Figure 3.

The catalyst to be used in the reforming operation may be either introduced into line Ia by a feeder as previously described or may be positioned in the coils of reforming coils 1. The reaction chamber 29 may be charged-with contact mass catalysts or the catalysts may be introduced into line 9 to pass with the vapors through line 9'. It is preferred, however, in the structure shown in Figure 3, to charge reaction chamber 29 with catalysts.

In the operation according to the flow sheet shown in Figure 4, the polymerization and the reforming operation are carried out in one zone. The feed which consists of kerosene and gasoline fractions containing added thereto propane, butane, propene, butene, ethane, and ethylene produced as previously described, is passed under pressure together with the catalyst, if an entrained catalyst be used, through lines I and 20 and through heater exchange 3a, line 4, coil 1 `positioned in chamber 8. Instead of using an entrained catalyst I may use coils charged with catalytic mass. Polymerized and reformed gasoline is then doused by contact with heavy fuel oil entering through passed into the heat exchange 3b and through separator |2. The heavy fractions are withdrawn through line I3 and the vapors are passed through mist extractor and fractionator elements |2b and washed with oil introduced through |20, to separate the heavy ends of the vapors. The vapors then pass through line I5 to the fractionator 33 in which the heavy oil is withdrawn through line 28 and vapors reiiuxed by reflux produced by cooler 42. The polymer and reformed gasoline are withdrawn into side stream receiver 39, and passed by pump 40 through the heater 4| and introduced into the stabilizer 46. The uncondensed vapors through line 43 are also introduced into stabilizer 46 by compressor 43a. In the stabilizer the vapors are separated into a stabilized gasoline, withdrawn through 5| and cooler 53. 'I'he bottoms are heated by circulating through line 41, heater 49 and line 50. Reflux is obtained by the condensation of the vapors, withdrawn through by-pass 54, valve 55, condenser 54h and condensate collected in 54' returned through 54a as a reflux. Liquid fraction withdrawnthrough 50a contains the hydrocarbons ranging from butanes and butylenes,

propane and propylenes to ethane and ethylene.

These are recirculated through line 20 to be sent to reformer coils 1.

The temperature chosen in Figure 4 in operating with fullers earth may be in theneighborhood of 8401020 F.; thepressure in the neighborhood of 500-5000 lbs. The other conditions will follow those described with regard to Figure 3.

In AView of the fact that the polymerization reaction using certain catalysts as previously described, operates best at temperatures lower than the reforming operation, the for-m of heater shown Figure 5 provides for reaction zones of alternatively high and low temperatures in which the reaction mass is first passed through high temperature and then low temperature zones. 'I'he desired catalysts ymay be separated.4 The reforming catalysts may be positioned in the high temperature zone and polymerizing catalysts in the low temperature zone or the mixed catalysts may be used in both zones. The furnace 8 is divided by vertical partition walls |00 to form chambers 8a and 8b. 'I'he coils 1 are positioned in both zones, the flow being first passed through the coils in zone 8a and then zone 8b, and then zone 8a, etc., as shown until the vapors exit.

l The furnace is heated by burner |0| in combustion tunnel |0|a. and the gases escape through conduit |02. The combustion gases may be split by proper manipulation of dampers |03 and |04. A portion may be passed through conduit |05 passing into the flue |09 leading to the stack. Combustion air which is also usedfor cooling the4 chamber 8b is circulated through conduits I I0 and by fan ||2 passed through low temperature zone 8b and conduit ||3. A portion of the thus preheated air is split by proper manipulation of dampers I|4 and |I5, and passes through conduit I|6 to provide combustion air for burner 0|. In this fashion cold air, and if desired, flue gases recycled by the circulation of the portion of combustion stream from conduit |02, is circulated over the coils in chamber 3. Chamber 8b is therefore maintained at considerably lower temperature from chamber `0a. Wall |00 is preferably made of heat insulating material which is suitable for highjemperature operation such as re brick or diatomaceous earth bricks. By proper circulation of air any desired difference in temperature may be maintained. It is understood that instead of passing the reaction material rst through the coils in chamber 8a, then through chamber 8b and then through chamber 8a, etc., the vapors may be passed in any number of passes through the coils in chamber 8a, and then to chamber 8b to pass in the chosen number of passes. Thus, the vapors may be passed to chamber 8a to carry on the reforming reaction, and then passed through chamber, 8bfor polymerization. The gases and vapors after exiting from chamber 8b are then treated as shown in Figure 4. It will be understood that the furnace construction and now shown in Figure 5 may also be used in place of the furnaces shown in Figures l, 2 and 3.

In operating the reaction in Figure 5, the coils in chamber'a shall be maintained from 930- 1020 F. while the coils in chamber 9b shall be at about S40-720 F. In this case the catalyst may be fullers earth or activated fullers earth, or

aluminum oxide, or the precipitated oxide previously described. v

While the-descriptions of the preferred opera tion in Figs. 4 and5 are given with relation to catalyzedv reactions, the process there described may also becarrled out as an uncatalyzed reaction by omitting the catalyst. In the case of Fig. 5 uncatalyzed operation, the temperature plane in zone 8a should be relatively higher in the range of 1000-1300 F. and the temperature in zone 8b should be lower in the range of '150- 950 F.

Figure 6 shows a modification wherein the reforming and polymerization reaction is separated, and the polymerized and reformed materials are combined for treatment to produce a blended, stabilized, polymerized and reformed gasoline. Feed composed of petroleum fractions, for instance kerosene and gasoline, is introduced through line I, into fractionator I3. A side cut having an intermediate boiling range is with` drawn through vline Ia by pump 2 and sent through heat exchange 3a into reforming charnber I positioned in furnace 8. Reformed gasoline is then contacted with the dousing oil composed of fuel oil introduced through II. where it is partially cooled and then passed through heat exchange coil 3b. It meets in line 9 polymerized material introduced through line 90. 'I'he mixture of polymerized and reformed gasoline passes into separator I2 and through mist extractor I2b. The heavy ends are withdrawn through I3 and the uncondensed vapors of a temperature from 425450 F. are removed through line I5, then passed into the stripper and fractionator 33 where, by the aid of the feed I and the reboiler 33a and reflux coil 42 in fractionating chamber 33h, it is fractionated into heavy ends 28, recycle stock Ia and the side cut of reformed and polymerized gasoline withdrawn through line 39a. Reux is provided by coil 42. The uncondensed vapors are withdrawn through line 43. The side cut 39a is passed by pump 40 into heater 4I and into the stabilizer 46. The uncondensed vapors are passed by pump 43a, line 43, into the stabilizer 46. In this stabilizer the gasoline is stabilized by the aid of reboiler 46a and reflux provided by the condensation of gases withdrawn through valve 55, lines 54 and 54a and condenser 54h. Stabilized gasoline is withdrawn through 5I, and liquefied gases containing the butanes, propanes, butylenes, propylenes, ethane and ethylene pass through line 56a into collecting chamber 56 for recycling by pump 51 through line into line 80. In this line it meets additional like materials through line 81. The commingled gases are then passed into heat exchanger 9Ia into polymerization coll 9| positioned in furnace 92. 'I'he hot gases are doused by mixing with a dousing medium such as gas oil, fuel oil, or kerosene, or gasoline introduced through 93 and passed through exchanger SIb and through 90 as previously described.

The reaction in coil 'I may be uncatalyzed or catalyzed. If catalyzed, the catalyst may be any one of the reforming catalyst hereinabove indicated. The temperature may be regulated independently of coil 9i. The pressure in coil 9| may be independently controlled by regulating valve 80a. The temperature in coil 1 may, depending upon the catalyst, be' from S40-1050* F. and the pressures from about 150-500 lbs. if uncatalyzed, the temperature may be between 900- 1250 F., while in coil 9|, the pressures may be around 500-5000 lbs., and the temperatures from aassysaf lao-75o"` F., depending @oaths lcatalyst employed. Any of the poiymerizingcatalysts prcviously.. described may be employed. Mixed catalyst slurry .is removed throughchambe'r I2. This will depend on the catalystand stock chosen as will be understood from what has been said previously. If vthe reactions in coil II' vare uncata-4 lyzed. the temperature may range. from 8507-950 The foregoing description of the several modiilcations of my invention described above'are not to be considered as limiting since many varia- Y tions may be made within the scope of the following claims by those skilled in the art without vdeparting fromv the spirit thereof.

The present applicationis a division of my copending applicationSerial No. 35,702, filed August 12, 1935.

1. A process for producing reformed and polymer gasoline which comprises heating hydrocarbons within theggasoline range in the presence of a reforming catalyst at a temperature within the range of 8401060 F. and at a pressure within the range of 'I5-1500 lbs. to reform said gasoline range hydrocarbons, separating reformed gasoline fractions at a temperature of approximately 400-450 F. from the heated products of reforming contacting the reformed gasoline fractions produced by said reforming operation in the presence of unsaturated added hydrocarbons of four and less carbon atoms with a polymerization catalyst at a temperature ranging from 570-840" F. but at a temperature lower than said reforming operation under a pressure ranging from 75-1500 lbs. to polymerize added normally gaseous hydrocarbon fractions in the presence of gasoline fractions formed by the reforming operation, and separating a mixture of polymer and reformed gasoline thus produced.

2. A process for the production of reformed and polymer gasoline which comprises heating a mixture of hydrocarbons including hydrocarbons in the gasoline range having an end point not to exceed 650 F. to an elevated gasoline reforming temperature by passing said mixture in a confined stream without separation of vapor, dousing and cooling said heated vapors by commingling said vapors with fuel oil, and separating a vapor of reformed gasoline fractions at a temperature of about 40G-500 F. from the mixture of fuel oil and products of reforming, introducing normally gaseous hydrocarbons into said vapor stream and passing said mixture through a polymerizing zone maintained at a temperature lower than said reforming operation and polymerizing said normally gaseous hydrocarbons in the presence of said gasoline fractions in said polymerizing zone to produce polymer and reformed gasoline.

3. A process according to claim 2 wherein the normally gaseous hydrocarbons are introduced under a pressure sufficient to maintain them liquid and are expanded into the gasoline vapor stream to cool said vapor by the evaporation and expansion of said normally gaseous hydrocarbons.

4. A process as in claim 1 in which the reforming and polymerization catalysts have substantially the same chemical composition.

5. A'A process as in claim 1 wherein the mixture exiting from the reforming operation is contacted with fresh catalyst added to the flowing stream and the thus produced mixture subjected to the polymerization operation.

6. A process for producing reformed and polymer gasoline which comprises heating hydrocarbons within the gasoline range in the presence of a reforming catalyst at a temperature and pressure sufficient to reform said gasoline range hydrocarbons, separating reformed gasoline fractions at a temperature of approximately MiO-450 F. from the heated products of reforming. contacting the reformed gasoline fractions produced by said reforming operation in the presence of unsaturated added hydrocarbons of four and less carbon atoms with a polymerization catalyst under pressure and at a temperature lower than said reforming temperature to polymerize the added normally gaseous hydrocarbon fractions in the presence of gasoline fractions formed by the reforming operation and separating a mixture of polymer and reformed gasoline thus produced.

7. A process for the production of reformed and polymer gasoline which comprises heating a mixture of hydrocarbons including hydrocarbons in the gasoline range having an end point not to exceed 650 F. to an elevated gasoline reforming temperature by passing said mixture in a confined stream without separation of vapor, cool- 

